Lithium-aluminum-phosphorus-silicon-oxide molecular sieve compositions

ABSTRACT

Molecular sieve compositions having three-dimensional microporous framework structures of LiO 2 , AlO 2 , PO 2  and SiO 2  tetrahedral oxide units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula: 
     
         mR: (Li.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 
    
     wherein &#34;R&#34; represents at least one organic templating agent present in the intracrystalline pore system; &#34;m&#34; represents the molar amount of &#34;R&#34; present per mole of (Li w  Al x  P y  Si z )O 2  ; and &#34;w&#34;, &#34;x&#34;, &#34;y&#34; and &#34;z&#34; represent the mole fractions of lithium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. Their use as adsorbents, catalysts, etc. is also disclosed.

This application is a continuation of application Ser. No. 847,227,filed Apr. 2, 1986, now abandoned, which in turn is acontinuation-in-part of our copending application Ser. No. 599,952 filedApr. 13, 1984 and now abandoned.

FIELD OF THE INVENTION

The instant invention relates to a novel class of crystallinemicroporous molecular sieves and to the method of their preparation. Theinvention relates to novel lithium-aluminum-phosphorus-silicon-oxidemolecular sieves containing framework tetrahedral oxide units oflithium, aluminum, phosphorus and silicon. These compositions may beprepared hydrothermally from gels containing reactive compounds oflithium, aluminum, phosphorus and silicon capable of forming frameworktetrahedral oxides, and preferably at least one organic templating agentwhich functions in part to determine the course of the crystallizationmechanism and the structure of the crystalline product.

BACKGROUND OF THE INVENTION

Molecular sieves of the crystalline alumino-silicate zeolite type arewell known in the art and now comprise over 150 species of bothnaturally-occurring and synthetic compositions. In general thecrystalline zeolites are formed from corner-sharing AlO₂ and SiO₂tetrahedra and are characterized by having pore openings of uniformdimensions, having a significant ion-exchange capacity and being capableof reversibly desorbing an adsorbed phase which is dispersed throughoutthe internal voids of the crystal without displacing any atoms whichmake up the permanent crystal structure. Other crystalline microporouscompositions which are not zeolitic, i.e. do not contain AlO₂ tetrahedraas essential framework constituents, but which exhibit the ion-exchangeand/or adsorption characteristics of the zeolites are also known. Metalorganosilicates which are said to posses ion-exchange properties, haveuniform pores and are capable of reversibly adsorbing molecules havingmolecular diameters of about 6Å or less, are reported in U.S. Pat. No.3,941,871 issued Mar. 2, 1976 to Dwyer et al. A pure silica polymorph,silicalite, having molecular sieving properties and a neutral frameworkcontaining neither cations nor cation sites is disclosed in U.S. Pat.No. 4,061,724 issued Dec. 6, 1977 to R. W. Grose et al.

A recently reported class of microporous compositions and the firstframework oxide molecular sieves synthesized without silica, are thecrystalline aluminophosphate compositions disclosed un U.S. Pat. No.4,310,440 issued Jan. 12, 1982 to Wilson et al. These materials areformed from AlO₂ and PO₂ tetrahedra and have electrovalently neutralframeworks as in the case of silica polymorphs. Unlike the silicamolecular sieve, silicalite, which is hydrophobic due to the absence ofextra-structural cations, the aluminophosphate molecular sieves aremoderately hydrophilic, apparently due to the difference inelectronegativity between aluminum and phosphorus. Theirintracrystalline pore volumes and pore diameters are comparable to thoseknown for zeolites and silica molecular sieves.

In U.S. Pat. No. 4,440,871, there is described a novel class ofsilicon-substituted alumino-phosphates which are both microporous andcrystalline. The materials have a three dimensional crystal framework ofPO₂ ⁺, AlO₂ ⁻ and SiO₂ tetrahedral units and, exclusive of any alkalimetal or calcium which may optionally be present, an as-synthesizedempirical chemical composition on an anhydrous basis of:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3, the maximum value in each case depending upon the moleculardimensions of the templating agent and the available void volume of thepore system of the particular silicoaluminophosphate species involved;and "x", "y", and "z" represent the mole fractions of silicon, aluminumand phosphorus, respectively, present as tetrahedral oxides. The minimumvalue for each of "x", "y", and "z" is 0.01 and preferably 0.02. Themaximum value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52.These silicoaluminophosphates exhibit several physical and chemicalproperties which are characteristic of aluminosilicate zeolites andaluminophosphates.

In U.S. Pat. No. 4,500,651, there is described a novel class oftitanium-containing molecular sieves whose chemical composition in theass-synthesized and anhydrous form is represented by the unit empiricalformula:

    mR:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Ti_(x) Al_(y) P_(z))O₂ and has a value of betweenzero and about 5.0; and "x", "y" and "z" represent the mole fractions oftitanium, aluminum and phosphorus, respectively, present as tetrahedraloxides.

In U.S. Pat. No. 4,567,029, there is described a novel class ofcrystalline metal alumino-phosphates having three-dimensionalmicroporous framework structures of MO₂, AlO₂ and PO₂ tetrahedral unitsand having an empirical chemical composition on an anhydrous basisexpressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R" presentper mole of (M_(x) Al_(y) P_(z))O₂ and has a value of from zero to 0.3;"M" represents at least one metal of the group magnesium, manganese,zinc and cobalt; "x", "y", and "z" represent the mole fractions of themetal "M", aluminum and phosphorus, respectively, present as tetrahedraloxides.

In U.S. Pat. No. 4,544,143, there is described a novel class ofcrystalline ferroaluminophosphates having a three-dimensionalmicroporous framework structure of FeO₂, AlO₂ and PO₂ tetrahedral unitsand having an empirical chemical composition on an anhydrous basisexpressed by the formula

    mR:(Fe.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Fe_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3; and "x", "y" and "z" represent the mole fractions of the iron,aluminum and phosphorus, respectively, present as tetrahedral oxides.

The instant inventions relates to new molecular sieve compositionscomprising framework tetrahedral units of LiO₂ ⁻³, AlO₂ ⁻, PO₂ ⁺ andSiO₂.

DESCRIPTION OF THE FIGURES

FIG. 1 is a ternary diagram wherein parameters relating to the instantcompositions are set forth as mole fractions.

FIG. 2 is a ternary diagram wherein parameters relating to preferredcompositions are set forth as mole fractions.

FIG. 3 is a ternary diagram wherein parameters relating to the reactionmixtures employed in the preparation of the compositions of thisinvention are set forth as mole fractions.

SUMMARY OF THE INVENTION

The instant invention relates to a new class oflithium-aluminum-phosphorus-silicon-oxide molecular sieves having acrystal framework structure of LiO₂ ⁻³, AlO₂ ⁻, PO₂ ⁺ and SiO₂tetrahedral oxide units. These new molecular sieves exhibition-exchange, adsorption and catalytic properties and, accordingly, findwide use as adsorbents and catalysts. The members of this novel class ofcompositions have crystal framework structures of LiO₂ ⁻³, AlO₂ ⁻, PO₂ ⁺and SiO₂ tetrahedral units and have an empirical chemical composition onan anhydrous basis expressed by the formula:

    mR:(Li.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Li_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of lithium, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides. These molecular sieve compositionscomprise crystalline molecular sieves having a three-dimensionalmicroporous framework structure of LiO₂ ⁻³, AlO₂ ⁻, PO₂ ⁺ and SiO₂tetrahedral units. The instant molecular sieve compositions arecharacterized in several ways as distinct from heretofore knownmolecular sieves, including the aforementioned ternary compositions. Theinstant molecular sieves are characterized by the enhanced thermalstability of certain species and by the existence of species heretoforeunknown for binary and ternary molecular sieves.

The molecular sieves of the instant invention will be generally referredto by the acronym "LiAPSO" to designate the framework of LiO₂ ⁻³, AlO₂⁻, PO₂ ⁺ and SiO₂ tetrahedral units. Actual class members will beidentified by denominating the various structural species which make upthe LiAPSO class by assigning a number and, accordingly, are identifiedas "LiAPSO-i" wherein "i" is an integer. This designation is anarbitrary one and is not intended to denote structural relationship toanother material(s) which may also be characterized by a numberingsystem.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention relates to a new class oflithium-aluminum-phosphorus-silicon-oxide molecular sieves comprising acrystal framework structure of LiO₂ ⁻³, AlO₂ ⁻, PO₂ ⁺ and SiO₂tetrahedral oxide units. These new molecular sieves exhibition-exchange, adsorption and catalytic properties and, accordingly, findwide use as adsorbents and catalysts.

The LiAPSO molecular sieves of the instant invention comprise aframework structure of LiO₂ ⁻³, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral unitshaving an empirical chemical composition on an anhydrous basis expressedby the formula:

    mR:(Li.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Li_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than about 0.15; and"w", "w", "y" and "z" represent the mole fractions of lithium, aluminum,phosphorus and silicon, respectively, present as tetrahedral oxides. Themole fractions "w", "x", "y" and "z" are generally defined as beingwithin the pentagonal compositional area defined by points A, B, C, Dand E of the ternary diagram of FIG. 1. Points A, B, C, D and E of FIG.1 have the following values for "w", "x", "y", and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z + w                                           ______________________________________                                        A        0.60          0.38   0.02                                            B        0.38          0.60   0.02                                            C        0.01          0.60   0.39                                            D        0.01          0.01   0.98                                            E        0.60          0.01   0.39                                            ______________________________________                                    

In a preferred subclass of the LiAPSO molecular sieves the values of"w", "x", "y" and "z" in the above formula are within the hexagonalcompositional area defined by the points a, b, c, d, e and f of theternary diagram which is FIG. 2 of the drawings, said points a, b, c, d,e and f representing the following values for "w", "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z + w                                           ______________________________________                                        a        0.60          0.38   0.02                                            b        0.38          0.60   0.02                                            c        0.01          0.60   0.39                                            d        0.01          0.39   0.60                                            e        0.39          0.01   0.60                                            f        0.60          0.01   0.39                                            ______________________________________                                    

Especially preferred molecular sieves of this invention are those inwhich w+z is not greater than about 0.20.

The LiAPSOs of this invention are useful as adsorbents, catalysts,ion-exchangers, and the like in much the same fashion asaluminosilicates have been employed heretofore, although their chemicaland physical properties are not necessarily similar to those observedfor aluminosilicates.

LiAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources oflithium, aluminum, phosphorus and silicon, preferably an organictemplating, i.e., structure-directing agent, preferably a compound of anelement of Group VA of the Periodic Table, and/or optionally an alkalior other metal. The reaction mixture is generally placed in a sealedpressure vessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenouspressure, at a temperature between 50° C. and 250° C., and preferablybetween 100° C. and 200° C., until crystals of the LiAPSO product areobtained, usually for a period of from several hours to several weeks.Crystallization times of from about 2 hours to about 30 days aregenerally employed with from about 4 hours to about 20 days, andpreferably about 1 to about 10 days, being typically employed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the LiAPSO compositions of the instant invention, it ispreferred to employ a reaction mixture composition expressed in terms ofthe molar ratios as follows:

    aR:(Li.sub.s Al.sub.t P.sub.u Si.sub.v)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero (0) to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and desirably not greater than 0.5; "b" has a value of fromzero (0) to about 500, preferably between about 2 and about 300,desirably not greater than about 20, and most desirably not greater thanabout 10; and "s", "t", "u" and "v" represent the mole fractions oflithium, aluminum, phosphorus and silicon, respectively, and each has avalue of at least 0.01. In a preferred embodiment the reaction mixtureis selected such that the mole fractions "s", "t", "u" and "v" aregenerally defined as being within the pentagonal compositional areadefined by points F, G, H, I and J of the ternary diagram of FIG. 3.Points F, G, H, I and J of FIG. 3 have the following values for "s","t", "u" and "v":

    ______________________________________                                               Mole Fraction                                                          Point    t             u      (v + s)                                         ______________________________________                                        F        0.60          0.38   0.02                                            G        0.38          0.60   0.02                                            H        0.01          0.60   0.39                                            I        0.01          0.01   0.98                                            J        0.60          0.01   0.39                                            ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "s", "t", "u" and "v" suchthat (w+x+y+z)=1.00 mole, whereas in the examples the reaction mixturesare expressed in terms of molar oxide ratios normalized to the moles ofP₂ O₅. This latter form is readily converted to the former form byroutine calculations by dividing the number of moles of each component(including the template and water) by the total number of moles oflithium, aluminum, phosphorus and silicon which results in normalizedmole fractions based on total moles of the aforementioned components.

In forming reaction mixtures from which the instant molecular sieves areformed the organic templating agent can be any of those heretoforeproposed for use in the synthesis of conventional zeolitealuminosilicates. In general these compounds contain elements of GroupVA of the Periodic Table of Elements, particularly nitrogen, phosphorus,arsenic and antimony, preferably nitrogen or phosphorus and mostpreferably nitrogen, which compounds also contain at least one alkyl oraryl group having from 1 to 8 carbon atoms. Particularly preferredcompounds for use as templating agents are the amines, quaternaryphosphonium and quaternary ammonium compounds, the latter two beingrepresented generally by the formula R₄ X⁺ wherein "X" is phosphorus ornitrogen and each R is an alkyl or aryl group containing from 1 to 8carbon atoms. Polymeric quaternary ammonium salts such as [(C₁₄ H₃₂N₂)(OH₂ ]_(x) wherein "x" has a value of at least 2 are also suitablyemployed. The mono, di- and tri-amines are advantageously utilized,either alone or in combination with a quaternary ammonium compound orother templating compound. Mixtures of two or more templating agents caneither produce mixtures of the desired LiAPSOs or the more stronglydirecting templating species may control the course of the reaction withthe other templating species serving primarily to establish the pHconditions of the reaction gel. Representative templating agents includetetramethylammonium; tetraethylammonium; tetrapropylammonium; andtetrabutylammonium ions; tetrapentylammonium ions; di-n-propylamine;tripropylamine; triethylamine; triethanolamine; piperidine;cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine;N,N-dimethylethanolamine; choline; N,N'-dimethylpiperazine;1,4-diazabicyclo (2,2,2,) octane; N-methyldiethanolamine,N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine;N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine;quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine;t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Notevery templating agent will direct the formation of every species ofLiAPSO, i.e., a single templating agent can, with proper manipulation ofthe reaction conditions, direct the formation of several LiAPSOcompositions, and a given LiAPSO composition can be produced usingseveral different templating agents.

The reactive phosphorus source is preferably phosphoric acid, butorganic phosphates such as triethyl phosphate have been foundsatisfactory, and so also have crystalline or amorphousaluminophosphates such as the AlPO₄ composition of U.S. Pat. No.4,310,440. Organophosphorus compounds, such as tetrabutylphosphoniumbromide, do not, apparently, serve as reactive sources of phosphorus,but these compounds do function as templating agents. Conventionalphosphorus salts, such as sodium metaphosphate, may be used, at least inpart, as the phosphorus source, but are not preferred.

Almost any reactive silicon source may be employed such that SiO₂tetrahedral units are formed in situ. The reactive silicon source may besilica in the form of a silica sol, may be a fumed silica or may beother conventional sources of silica used in zeolite synthesis such asreactive solid amorphous precipitated silicas, silica gel, alkoxides ofsilicon, tetraalkyl orthosilicates (for example, tetraethylorthosilicate), silicic acid, alkali metal silicates and the like.

The preferred aluminum source is either an aluminum alkoxide, such asaluminum isoproproxide, or pseudoborehmite. The crystalline or amorphousaluminophosphates which are a suitable source of phosphorus are, ofcourse, also suitable sources of aluminum. Other sources of aluminumused in zeolite synthesis, such as gibbsite, sodium aluminate andaluminum trichloride, can be employed but are not preferred.

The reactive source of lithium can be introduced into the reactionsystem in any form which permits the formation in situ of a reactiveform of lithium, i.e., reactive to form the framework tetrahedral oxideunit of lithium. Compounds of lithium which may be employed includeoxides, alkoxides, hydroxides, chlorides, bromides, iodides, sulfates,nitrates, carboxylates (e.g., acetates) and the like. Phosphates canalso be employed.

While not essential to the synthesis of LiAPSO compositions, stirring orother moderate agitation of the reaction mixture and/or seeding thereaction mixture with seed crystals of either the LiAPSO species to beproduced or a topologically similar aluminophosphate, aluminosilicate ormolecular sieve composition, facilitates the crystallization procedure.

After crystallization the LiAPSO product may be isolated andadvantageously washed with water and dried in air. The as-synthesizedLiAPSO generally contains within its internal pore system at least oneform of the templating agent employed in its formation. Most commonlythe organic moiety derived from an organic template is present, at leastin part, as a charge-balancing balancing cation as is generally the casewith as-synthesized aluminosilicate zeolites prepared fromorganic-containing reaction systems. It is possible, however, that someor all of the organic moiety is an occluded molecular species in aparticular LiAPSO species. As a general rule the templating agent, andhence the occluded organic species, is too large to move freely throughthe pore system of the LiAPSO product and must be removed by calciningthe LiAPSO at temperatures of 200° C. to 700° C., and preferably 350° C.to 600° C. to thermally degrade the organic species. In a few instancesthe pores of the LiAPSO product are sufficiently large to permittransport of the templating agent, particularly if the latter is a smallmolecule, and accordingly complete or partial removal thereof can beaccomplished by conventional desorption procedures such as are carriedout in the case of zeolites. It will be understood that the term"as-synthesized" as used herein does not include the condition of theLiAPSO phase wherein the organic moiety occupying the intracrystallinepore system as a result of the hydrothermal crystalline process has beenreduced by post-synthesis treatment such that the value of "m" in thecomposition formula:

    mR:(Li.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

has a value of less than 0.02. The other symbols of the formula are asdefined hereinabove. In those preparations in which an alkoxide isemployed as the source of lithium, aluminum, phosphorus and/or silicon,the corresponding alcohol is necessarily present in the reaction mixturesince it is a hydrolysis product of the alkoxide. It has not beendetermined whether this alcohol participates in the synthesis process asa templating agent. For the purposes of this application, however, thisalcohol is arbitrarily omitted from the class of templating agents, evenif it is present in the as-synthesized LiAPSO material.

Since the present LiAPSO compositions are formed from LIO₂, AlO₂, PO₂and SiO₂, tetrahedral units which, respectively, have a net charge of-1, -1, +1 and 0, the matter of cation exchangeability is considerablymore complicated than in the case of zeolitic molecular sieves in which,ideally, there is a stoichiometric relationship between AlO₂ ⁻tetrahedra and charge-balancing cations. In the instant compositions, anAlO₂ ⁻ tetrahedron can be balanced electrically either by associationwith a PO₂ ⁺ tetrahedron or a simple cation such as an alkali metalcation other than lithium, a cation of lithium present in the reactionmixture, a proton (H⁺) or an organic cation derived from the templatingagent. Similarly, an LiO₂ ⁻³ tetrahedron can be balanced electrically byassociation with PO₂ ⁺ tetrahedra, a cation of lithium present in thereaction mixture, a simple cation such as an alkali metal cation otherthan lithium, organic cations derived from the templating agent, aproton (H⁺) or other divalent or polyvalent metal cations introducedfrom an extraneous source. It has also been postulated that non-adjacentAlO₂ ⁻ and PO₂ ⁺ tetrahedral pairs can be balanced by Na⁺ and OH--respectively [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS,Washington, DC (1971)].

The LiAPSO compositions of the present invention may exhibitcation-exchange capacity when analyzed using ion-exchange techniquesheretofore employed with zeolitic aluminosilicates and have porediameters which are inherent in the lattice structure of each speciesand which are at least about 3Å in diameter. Ion exchange of LiAPSOcompositions is ordinarily possible only after the organic moietypresent as a result of synthesis has been removed from the pore system.Dehydration to remove water present in the as-synthesized LiAPSOcompositions can usually be accomplished, to some degree at least, inthe usual manner without removal of the organic moiety, but the absenceof the organic species greatly facilitates adsorption and desorptionprocedures. The LiAPSO materials will have various degrees ofhydrothermal and thermal stability, some being quite remarkable in thisregard, and will function as molecular sieve adsorbents and hydrocarbonconversion catalysts or catalyst bases.

In preparing the LiAPSO composition it is preferred to use a stainlesssteel reaction vessel lined with an inert plastic material, e.g.,polytetrafluoroethylene, to avoid contamination of the reaction mixture.In general, the final reaction mixture from which each LiAPSOcomposition is crystallized is prepared by forming mixtures of less thanall of the reagents and thereafter incorporating into these mixturesadditional reagents either singly or in the form of other intermediatemixtures of two or more reagents. In some instances the reagents admixedretain their identity in the intermediate mixture and in other casessome or all of the reagents are involved in chemical reactions toproduce new reagents. The term "mixture" is applied in both cases.Further, it is preferred that the intermediate mixtures as well as thefinal reaction mixtures be stirred until substantially homogeneous.

X-ray patterns of reaction products are obtained by X-ray analysis,using standard X-ray powder diffraction techniques. The radiation sourceis a high-intensity, copper target, X-ray tube operated at 50 Kv and 40ma. The diffraction pattern from the copper K-alpha radiation andgraphite monochromator is suitably recorded by an X-ray spectrometerscintillation counter, pulse height analyzer and strip chart recorder.Flat compressed powder samples are scanned at 2° (2 theta) per minute,using a two second time constant. Interplanar spacings (d) in Angstromunits are obtained from the position of the diffraction peaks expressedas 2θ where θ is the Bragg angle as observed on the strip chart.Intensities were determined from the heights of diffraction peaks aftersubtracting background, "I_(o) " being the intensity of the strongestline or peak, and "I" being the intensity of each of the other peaks.Alternatively, the X-ray patterns may be obtained by use of computerbased techniques using copper K-alpha radiation, Siemens type K-805X-ray sources and Siemens D-500 X-ray powder diffractometers availablefrom Siemens Corporation, Cherry Hill, N.J.

As will be understood by those skilled in the art, the determination ofthe parameter 2 theta is subject to both human and mechanical error,which in combination, can impose an uncertainty of about ±0.4° on eachreported value of 2 theta. This uncertainty is, of course, alsomanifested in the reported values of the d-spacings, which arecalculated from the 2 theta values. This imprecision is generalthroughout the art and is not sufficient to preclude the differentiationof the present crystalline materials from each other and from thecompositions of the prior art. In some of the X-ray patterns reported,the relative intensities of the d-spacings are indicated by thenotations vs, s, m, w and vw which represent very strong, strong,medium, weak and very weak, respectively.

In certain instances hereinafter in the illustrative examples, thepurity of a synthesized product may be assessed with reference to itsX-ray powder diffraction pattern. Thus, for example, if a sample isstated to be pure, it is intended only that the X-ray pattern of thesample is free of lines attributable to crystalline impurities, not thatthere are no amorphous materials present.

The molecular sieves of the instant invention may be characterized bytheir X-ray powder diffraction patterns and such may have one of theX-ray patterns set forth in the following Tables A through W, whereinsaid X-ray patterns are for the as-synthesized form unless otherwisenoted. In most cases, the pattern of the corresponding calcined formwill also fall within the relevant table. However, in some cases theremoval of the occluded templating agent which occurs during calcinationwill be accompanied by sufficient relaxation of the lattice to shiftsome of the lines slightly outside the ranges specified in the relevanttable. In a small number of cases, calcination appears to cause moresubstantial distortion in the crystal lattice, and hence, moresignificant changes in the X-ray powder diffraction pattern.

                  TABLE A                                                         ______________________________________                                        (LiAPSO-5)                                                                    2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.2-7.7      12.28-11.48                                                                             m-vs                                                   19.4-19.9    4.58-4.46 w-m                                                    20.8-21.3    4.26-4.17 w-vs                                                   22.1-22.6    4.02-3.93 m-vs                                                   25.6-26.1    3.480-3.414                                                                             vw-m                                                   ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        (LiAPSO-11)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.8-8.2      11.19-10.85                                                                             m-s                                                    9.0-9.8      9.83-9.03 vw-vs                                                  12.8-13.6    6.92-6.51 vw-m                                                   19.9-20.5    4.46-4.33 m-s                                                    20.8-21.8    4.27-4.08 m-vs                                                   22.0-22.6    4.04-3.93 m-vs                                                   22.6-23.1    3.93-3.85 vw-vs                                                  23.1-23.5    3.85-3.79 w-vs                                                   ______________________________________                                    

                  TABLE C                                                         ______________________________________                                        (LiAPSO-14)                                                                   2θ     d(Å) Relative Intensity                                      ______________________________________                                        8.6-8.9      10.3-9.93                                                                              vs                                                      13.0         6.81     w                                                       21.9-22.2    4.06-4.00                                                                              w                                                       25.4         3.51     w                                                       27.5         3.24     w                                                       29.7         3.01     w                                                       ______________________________________                                    

                  TABLE D                                                         ______________________________________                                        (LiAPSO-16)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        11.3-11.6    7.83-7.63 w-vs                                                   18.55-18.9   4.78-4.70 vw-m                                                   21.85-22.2   4.07-4.00 m-vs                                                   22.8-23.3    3.900-3.818                                                                             w-m                                                    26.4-27.3    3.370-3.267                                                                             w-m                                                    29.6-29.9    3.018-2.988                                                                             w-m                                                    ______________________________________                                    

                  TABLE E                                                         ______________________________________                                        (LiAPSO-17)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.70-7.75    11.5-11.4 vs                                                     13.4         6.61      s-vs                                                    15.5-15.55  5.72-5.70 s                                                      19.65-19.7   4.52-4.51 w-s                                                    20.5-20.6    4.33-4.31 vs                                                      31.8-32.00  2.812-2.797                                                                             w-s                                                    ______________________________________                                    

                  TABLE F                                                         ______________________________________                                        (LiAPSO-18)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                         9.6-9.65    9.21-9.16 vs                                                      15.5-15.55  5.72-5.70 m                                                      16.9-17.1    5.25-5.19 m                                                      20.15-20.25  4.41-4.39 m                                                      20.95-21.05  4.24-4.22 m                                                      31.8-32.5    2.814-2.755                                                                             m                                                      ______________________________________                                    

                  TABLE G                                                         ______________________________________                                        (LiAPSO-20)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        13.8-14.2    6.42-6.23 m-vs                                                    19.6-20.15  4.53-4.41 m                                                      24.1-24.7    3.695-3.603                                                                             m-vs                                                   27.9-28.6    3.198-3.121                                                                             w                                                       31.3-32.05  2.861-2.791                                                                             w                                                      34.35-35.0   2.610-2.601                                                                             w-m                                                    ______________________________________                                    

                  TABLE H                                                         ______________________________________                                        (LiAPSO-31)                                                                   2θ     d(Å)   Relative Intensity                                    ______________________________________                                        8.4-9.5      10.53-9.31 w-s                                                   20.2-20.4    4.40-4.35  m                                                     22.0-22.1    4.040-4.022                                                                              m                                                     22.5-22.7    3.952-3.92 vs                                                    31.6-31.8    2.831-2.814                                                                              w-m                                                   ______________________________________                                    

                  TABLE J*                                                        ______________________________________                                        (LiAPSO-33)                                                                   2θ     d(Å) Relative Intensity                                      ______________________________________                                        9.25-9.55    9.56-9.26                                                                              w-m                                                     12.5-12.9    7.08-6.86                                                                              vs                                                      16.9-17.3    5.25-5.13                                                                              w-m                                                     20.45-20.9   4.34-4.25                                                                              w-m                                                     23.85-24.25  3.73-3.67                                                                              w-m                                                     26.05-26.35  3.42-3.38                                                                              w-m                                                     27.3-27.6    3.27-3.23                                                                              vs                                                      ______________________________________                                         *as-synthesized form                                                     

                  TABLE K*                                                        ______________________________________                                        (LiAPSO-33)                                                                   2θ     d(Å) Relative Intensity                                      ______________________________________                                        13.15-13.4   6.73-6.61                                                                              vs                                                      18.0-18.35   4.91-4.83                                                                              m                                                       18.4-18.6    4.82-4.77                                                                              m                                                       26.55-26.7   3.36-3.34                                                                              m                                                       32.0-32.1    2.80-2.79                                                                              m                                                       ______________________________________                                         *calcined form                                                           

                  TABLE L                                                         ______________________________________                                        (LiAPSO-34)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.3-9.8      9.51-9.03 m-vs                                                   12.6-13.2    7.03-6.71 w-m                                                    15.8-16.3    5.61-5.44 vw-m                                                   20.25-21.2   4.39-4.19 w-vs                                                   24.8-25.4     3.59-3.507                                                                             vw-m                                                   30.0-30.9    2.979-2.894                                                                             vw-m                                                   ______________________________________                                    

                  TABLE M                                                         ______________________________________                                        (LiAPSO-35)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        10.6-11.1    8.35-7.97 vw-vs                                                  13.1-13.7    6.76-6.46 vw-vs                                                  17.0-17.6    5.22-5.04 w-s                                                     20.6-21.25  4.31-4.18 vw-m                                                   21.6-22.3    4.11-3.99 m-vs                                                   28.1-28.8    3.175-3.100                                                                             vw-m                                                   ______________________________________                                    

                  TABLE N                                                         ______________________________________                                        (LiAPSO-36)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.45-8.0     11.14-11.05                                                                             vs                                                     8.1-8.3      10.91-10.65                                                                             w-m                                                    16.3-16.6    5.44-5.34 w-m                                                    18.9-19.4    4.70-4.57 w-m                                                    20.7-21.0    4.29-4.23 w-m                                                    ______________________________________                                    

                  TABLE O                                                         ______________________________________                                        (LiAPSO-37)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        6.1-6.3      14.49-14.03                                                                             vs                                                     15.5-15.7    5.72-5.64 w-m                                                    18.5-18.8    4.80-4.72 w-m                                                    23.5-23.7    3.79-3.75 w-m                                                    26.9-27.1    3.31-3.29 w-m                                                    ______________________________________                                    

                  TABLE P                                                         ______________________________________                                        (LiAPSO-39)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.2-9.6      9.61-9.21 m                                                      13.1-13.5    6.76-6.56 m                                                      17.8-18.4    4.98-4.82 w-m                                                    20.8-21.3    4.27-4.17 m-vs                                                    22.2-22.85   4.00-3.892                                                                             m-vs                                                    26.4-27.05  3.376-3.296                                                                             w-m                                                    ______________________________________                                    

                  TABLE Q                                                         ______________________________________                                        (LiAPSO-40)                                                                   2θ    d(Å)  Relative Intensity                                      ______________________________________                                        7.5-7.7     11.79-11.48                                                                             vw-m                                                    8.0-8.1     11.05-10.94                                                                               5-vs                                                  12.4-12.5   7.14-7.08  w-vs                                                   13.6-13.8   6.51-6.42 m-s                                                     14.0-l4.1   6.33-6.28 w-m                                                     27.8-28.0   3.209-3.187                                                                             w-m                                                     ______________________________________                                    

                  TABLE R                                                         ______________________________________                                        (LiAPSO-41)                                                                   2θ    d(Å)  Relative Intensity                                      ______________________________________                                        13.6-13.8   6.51-6.42 w-m                                                     20.5-20.6   4.33-4.31 w-m                                                     21.1-21.3   4.21-4.17 vs                                                      22.1-22.3   4.02-3.99 m-s                                                     22.8-23.0   3.90-3.86 m                                                       23.1-23.4   3.82-3.80 w-m                                                     25.5-25.9   3.493-3.44                                                                              w-m                                                     ______________________________________                                    

                  TABLE S                                                         ______________________________________                                        (LiAPSO-42)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.15-7.4     12.36-11.95                                                                              m-vs                                                   12.5-12.7   7.08-6.97 m-s                                                    21.75-21.9   4.09-4.06 m-s                                                     24.1-24.25  3.69-3.67 vs                                                     27.25-27.4   3.273-3.255                                                                             s                                                       30.05-30.25 2.974-2.955                                                                             m-s                                                    ______________________________________                                    

                  TABLE T                                                         ______________________________________                                        (LiAPSO-43)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        12.3-12.95   7.20-6.83 m-vs                                                   16.8-17.45   5.28-5.09 vw-w                                                   21.45-21.85  4.145-4.071                                                                             m-vs                                                   27.1-27.85   3.291-3.232                                                                             w-vs                                                   32.3-33.2    2.763-2.699                                                                             vw-m                                                   ______________________________________                                    

                  TABLE U                                                         ______________________________________                                        (LiAPSO-44)                                                                   2θ     d(Å)     Relative Intensity                                  ______________________________________                                        9.2-9.6      9.61-9.21    m- vs                                               15.9-16.3    5.57-5.44    vw- m                                               20.5-21.0    4.33-4.23    m- vs                                               24.3-25.1     3.66-3.548  w- m                                                30.5-31.1    2.931-2.876  vw- m                                               ______________________________________                                    

                  TABLE V                                                         ______________________________________                                        (LiAPSO-46)                                                                   2θ   d(Å)       Relative Intensity                                  ______________________________________                                        7.2-8.1    12.28 -10.92   vs                                                  12.9-13.6  6.86-6.51      vw                                                  21.2-22.2   4.19-4.501    vw- m                                                22.5-23.45                                                                               3.95-3.793    vw- m                                               26.6-27.9  3.351-3.198    vw- m                                               ______________________________________                                    

                  TABLE W                                                         ______________________________________                                        (LiAPSO-47)                                                                   2θ   d(Å)       Relative Intensity                                  ______________________________________                                        9.4-9.6    9.41-9.21      vs                                                  12.8-13.1  6.92-6.76      vw- m                                               16.0-16.3  5.54-5.44      vw- m                                               20.5-21.0  4.31-4.23      m- vs                                               24.6-25.3  3.613-3.526    vw- m                                               30.6-31.1  2.921-2.876    vw- m                                               ______________________________________                                    

The exact nature of the LiAPSO molecular sieves is not entirelyunderstood at present, although all are believed to contain LiO₂tetrahedra in the three-dimensional microporous crystal frameworkstructure. The low level of lithium present in some of the instantmolecular sieves makes it difficult to ascertain the exact nature of theinteractions among lithium, aluminum, phosphorus and silicon. As aresult, although it is believed that LiO₂ tetrahedra are substitutedisomorphously for AlO₂ or PO₂ tetrahedra, it is appropriate tocharacterize certain LiAPSO compositions by reference to their chemicalcompositions in terms of the molar rations of oxides, as has been donein some of the examples below.

The following examples are provided to further illustrate the inventionand are not intended to be limiting thereof:

EXAMPLE 1 Preparation of LiAPSO-5

(a) LiAPSO-5 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide ratios of the components of thereaction mixture, of:

1.0-2.0 TPA:0.05-0.2 Li₂ O:0.5-1.0 Al₂ O₃ : 0.5-1.0 P₂ O₅ :0.1-0.6 SiO₂:40-100 H₂ O

where "TPA" denotes tripropylamine.

The reaction mixture is digested by placing the reaction mixture in asealed stainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce LiAPSO-5 product.Solids are recovered by filtration, washed with water and dried in airat room temperature.

The LiAPSO-5 product's chemical analysis shows the LiAPSO-5 productcontains lithium, aluminum, phosphorus and silicon in amounts within thepentagonal compositional area defined by points A, B, C, D and E of FIG.1.

The X-ray powder diffraction pattern of a LiAPSO-5 product ischaracterized by the following data:

    ______________________________________                                        2θ   d(Å)       Relative Intensity                                  ______________________________________                                        7.2-7.7    12.28-11.48    m- vs                                               19.4-19.9  4.58-4.46      w- m                                                20.85-21.3 4.26-4.17      w- vs                                               22.1-22.6  4.02-3.93      m- vs                                               25.6-26.1  3.480-3.414    vw- m                                               ______________________________________                                    

(b) The X-ray powder diffraction pattern for a calcined LiAPSO-5 is alsocharacterized by the X-ray pattern of part (a).

(c) When the calcined LiAPSO-5 of part (b) is utilized in adsorptioncapacity studies using a standard McBain-Bakr gravimetric adsorptionapparatus the measurements are made on a sample after activation at 350°C. in a vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                Kinetic    Pressure          Wt. %                                    Adsorbate                                                                             Diameter (Å)                                                                         (Torr)    Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2 3.46       100       -183    7                                        O.sub.2 3.46       750       -183    10                                       Neopentane                                                                            6.2        700         24    4                                        H.sub.2 O                                                                             2.65       4.3         24    4                                        H.sub.2 O                                                                             2.65       20.0        24    12                                       ______________________________________                                         *typical amount adsorbed   The pore diameter of LiAPSO-5 is greater than      about 6.2 Å.

EXAMPLE 2 Preparation of LiAPSO-11

(a) LiAPSO-11 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide ratios of the components of thereaction mixture, of:

1.0-2.0 DPA:0.05-0.2 Li₂ O:0.5-1.0 Al₂ O₃ : 0.5-1.0 P₂ O₅ :0.1-0.6 SiO₂:40-100 H₂ O

where "DPA" denotes di-n-propylamine.

The reaction mixture is digested by placing the reaction mixture in asealed stainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce LiAPSO-11 product.Solids are then recovered by filtration, washed with water and dried inair at room temperature.

The LiAPSO-11 product's chemical analysis shows the LiAPSO-11 productcontains lithium, aluminum, phosphorus and silicon in amounts within thepentagonal compositional area defined by points A, B, C, D and E of FIG.1.

The X-ray powder diffraction pattern of a LiAPSO-11 product ischaracterized by the following data:

    ______________________________________                                        2θ  d(Å)       Relative Intensity                                   ______________________________________                                        7.8-8.2   11.19-10.85    m- s                                                 9.2-9.8   9.83-9.03      vw- vs                                               12.8-13.6 6.92-6.51      vw- m                                                19.9-20.5 4.46-4.33      m- s                                                 20.8-21.8 4.27-4.08      m- vs                                                22.0-22.6 4.04-3.93      m- vs                                                22.6-23.1 3.93-3.85      vw- vs                                               23.1-23.5 3.85-3.79      w- vs                                                ______________________________________                                    

(b) The X-ray powder diffraction pattern for a calcined LiAPSO-11 isalso characterized by the X-ray pattern of part (a).

(c) When the calcined LiAPSO-11 of part (b) is utilized in adsorptioncapacity studies using a standard McBain-Bakr gravimetric adsorptionapparatus the measurements are made on a sample after activation at 350°C. in a vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2  3.46       100      -183    5                                        O.sub.2  3.46       750      -183    6                                        Cyclohexane                                                                            6.0        90         24    4                                        H.sub.2 O                                                                              2.65       4.3        24    6                                        H.sub.2 O                                                                              2.65       20         24    8                                        ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of LiAPSO-11 is about 6Å.

EXAMPLE 3 Preparation of LiAPSO-17

(a) LiAPSO-17 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide ratios of the components of thereaction mixture, of:

1.0-2.0 QN:0.05-0.02 Li₂ O:0.5-1.00 Al₂ O₃ : 0.5-1.0 P₂ O₅ :0.1-0.6 SiO₂:40-100 H₂ O

where "QN" denotes quinuclidine.

The reaction mixture is digested by placing the reaction mixture in asealed stainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce LiAPSO-17 product.Solids are then recovered by filtration, washed with water and dried inair at room temperature.

The LiAPSO-17 product's chemical analysis shows the LiAPSO-17 productcontains lithium, aluminum, phosphorus and silicon in amounts within thepentagonal compositional area defined by points A, B, C, D and E of FIG.1.

The X-ray powder diffraction pattern of a LiAPSO-17 product ischaracterized by the following data:

    ______________________________________                                        2θ     d(Å)     Relative Intensity                                  ______________________________________                                        7.70-7.75    11.5-11.4    vs                                                  13.4         6.61         s- vs                                                15.5-15.55  5.72-5.70    s                                                   19.65-19.7   4.52-4.51    w- s                                                20.5-20.6    4.33-4.31    vs                                                  31.8-32.0    2.812-2.797  w- s                                                ______________________________________                                    

(b) The X-ray powder diffraction pattern for a calcined LiAPSO-17 isalso characterised by the X-ray pattern of part (a).

(c) When the calcined LiAPSO-17 of part (b) is utilized in adsorptioncapacity studies using a standard McBain-Bakr gravimetric adsorptionapparatus the measurements are made on a sample after activation at 350°C. in a vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                Kinetic    Pressure          Wt. %                                    Adsorbate                                                                             Diameter (Å)                                                                         (Torr)    Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2 3.46       100       -183    10                                       O.sub.2 3.46       750       -183    12                                       n-butane                                                                              4.3        100         24     4                                       H.sub.2 O                                                                             2.65       4.3         24    13                                       H.sub.2 O                                                                             2.65       20          24    14                                       ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of LiAPSO-17 is about 4.3 Å.

EXAMPLE 4 Preparation of LiAPSO-31

(a) LiAPSO-31 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide rations of the components of thereaction mixture, of:

1.0-2.0 DPA:0.05-0.2 Li₂ O:0.5-1.0 Al₂ O₃ : 0.5-1.0 P₂ O₅ :0.1-0.6 SiO₂:40-100 H₂ O

where "DPA" denotes di-n-propylamine.

The reaction mixture is seeded with crystals of AlPO₄ -31 (U.S. Pat. No.4,310,440) and digested by placing the reaction mixture in a sealedstainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce LiAPSO-31 product.Solids are then recovered by filtration, washed with water and dried inair at room temperature.

The liAPSO-31 product's chemical analysis shows the LiAPSO-31 productcontains lithium, aluminum, phosphorus and silicon in amounts within thepentagonal compositional area defined by points A, B, C, D and E of FIG.1.

The X-ray powder diffraction pattern of a LiAPSO-31 product ischaracterized by the following data:

    ______________________________________                                        2θ     d(Å)  Relative Intensity                                     ______________________________________                                        8.4-9.5      10.53-9.31                                                                              w-s                                                    20.2-20.4    4.40-4.35 m                                                      22.0-22.1    4.040-4.022                                                                             m                                                      22.5-22.7    3.952-3.92                                                                              vs                                                     31.6-31.8    2.831-2.814                                                                             w-m                                                    ______________________________________                                    

(b) The X-ray powder diffraction pattern for a calcined LiAPSO-31 isalso characterized by the X-ray pattern of part (a).

(c) When the calcined LiAPSO-31 part (b) is utilized in adsorptioncapacity studies using a standard mcBain-Bakr gravimetric adsorptionapparatus the measurements are made on a sample after activation at 350°C. in a vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2  3.46       100      -183    4                                        O.sub.2  3.46       750      -183    6                                        Cyclohexane                                                                            6.0         90      24      3                                        Neopentane                                                                             6.2        700      24      3                                        H.sub.2 O                                                                              2.65       4.3      24      3                                        H.sub.2 O                                                                              2.65        20      24      10                                       ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of LiAPSO-31 is greater than about 6.2 Å.

EXAMPLE 5 Preparation of LiAPSO-34

(a) A reaction mixture was formed by combining 19.0 grams of hydratedaluminum oxide (in the form of a pseudo-boehmite phase comprising 75.1wt. percent of Al₂ O₃ and 24.0 wt. percent of H₂ O) and 1.4 grams oflithium orthophosphate with stirring. The resultant mixture was slowlyadded to 32.3 grams of 85 wt. percent orthophosphoric acid (H₃ PO₄) andthe resultant mixture was stirred until homogeneous. To this homogeneousmixture was added a mixture of 3.6 grams of a fumed silica 94.5 wt.percent SiO₂) and 51.5 grams of 40 wt. percent aqueoustetraethylammonium hydroxide (TEAOH), and the resultant mixture wasstirred until homogeneous. The composition of the final reaction mixturethus produced, expressed in terms of the molar oxide rations of thecomponents of the reaction mixture, was:

0.96 TEAOH:0.12 Li₂ O:0.96 Al₂ O₃ : 0.38 SiO₂ :1.00 P₂ O₅ :18 H₂ O.

This final reaction mixture was digested by sealing it in a stainlesssteel pressure vessel lined with polytetrafluoroethylene and heating itin an oven at 150° C. under autogenous pressure for 64 hours. The solidreaction product (which was determined by the analyses described belowto be LiAPSO-b 34) was recovered by centrifugation, washed with waterand dried in air at 100° C.

A sample of this solid reaction product was analyzed and the followingchemical analysis obtained:

    ______________________________________                                        Component     Weight percent                                                  ______________________________________                                        Carbon        9.1                                                             Nitrogen      1.3                                                             Li.sub.2 O    1.6                                                             Al.sub.2 O.sub.3                                                                            31.0                                                            SiO.sub.2     5.5                                                             P.sub.2 O.sub.5                                                                             41.7                                                            LOI*          20.7                                                            ______________________________________                                         *LOI indicates loss on ignition.                                         

The above chemical analysis corresponds to a product composition inmolar oxide ratios of:

0.32 TEAOH:0.18 Li₂ O:1.03 Al₂ O₃ : 0.31 SiO₂ :1.00 P₂ O₅ :1.27 H₂ O

which corresponds to an empirical chemical formula, on an anhydrousbasis, of:

0.07 TEAOH:(Li₀.08 Al₀.44 P₀.42 Si₀.07)O₂

so that the product contained lithium, aluminum, silicon and phosphorusin amounts within the pentagonal compositional area defined by points A,B, C, D and E of FIG. 1.

The X-ray powder diffraction pattern of the product, as synthesized, wascharacterized by the data in the following Table LA (Tables LA and LBbelow designate Tables of X-ray data which include all the peaksmentioned in Table L above):

                  TABLE LA                                                        ______________________________________                                        (LiAPSO-34)                                                                                       Relative Intensity                                        2θ     d(Å)                                                                             100 × I/I.sub.o                                     ______________________________________                                        9.56         9.25   100                                                       12.9         6.87   15                                                        14.1         6.26   18                                                        16.1         5.52   48                                                        18.0         4.92   23                                                        20.6         4.31   89                                                        22.3         3.99   5                                                         23.2         3.84   6                                                         25.3         3.53   26                                                        25.9         3.44   17                                                        27.7         3.22   7                                                         28.4         3.14   7                                                         29.7         3.01   5                                                         30.6         2.92   35                                                        31.3         2.86   21                                                        34.5         2.60   7                                                         36.4         2.47   5                                                         39.7         2.27   4                                                         43.5         2.08   5                                                         47.7         1.91   5                                                         49.1         1.86   7                                                         51.1         1.79   4                                                         53.3         1.72   3                                                         54.7         1.68   3                                                         ______________________________________                                    

A sample of the solid reaction product was calcined by heating it undernitrogen from ambient temperature to 500° C. over a period of 50minutes, then holding it at 500° C. under nitrogen for a further 90minutes. The calcined product has an X-ray diffraction patterncharacterized by the data in the following Table LB:

                  TABLE LB                                                        ______________________________________                                        (LiAPSO-34)                                                                                            Relative Intensity                                   2θ  d(Å)       100 × I/I.sub.o                                ______________________________________                                         9.67     9.15           100                                                  13.1      6.78            22                                                  14.2      6.22            2                                                   16.2      5.46            11                                                  18.O      4.92            8                                                   19.2      4.62            2                                                   20.8      4.27            27                                                  22.3      4.00            2                                                   23.3      3.82            3                                                   25.2      3.53            7                                                   26.1      3.41            7                                                   27.9      3.20            2                                                   28.4      3.14            1                                                   30.9      2.90            14                                                  31.3      2.86            7 (shoulder)                                        34.8      2.58            3                                                   36.3      2.47            2                                                   43.2      2.09            2                                                   48.1      1.89            2                                                   49.3      1.85            2                                                   51.1      1.79            2                                                   53.7      1.71            1                                                   54.8      1.68            1                                                   ______________________________________                                    

(b) A sample of the as-synthesized product produced in part (a) wassubjected to adsorption capacity studies using a standard McBain-Bakrgravimetric adsorption apparatus. Before being used in the adsorptiontests, the sample was calcined in situ by heating to 440° C. for 16hours in vacuum. The following data were generated in the adsorptionstudies:

    ______________________________________                                                Kinetic    Pressure          Wt. %                                    Adsorbate                                                                             Diameter (Å)                                                                         (Torr)    Temp, °C.                                                                      Adsorbed                                 ______________________________________                                        O.sub.2 3.46       106       -183    25.4                                     Neopentane                                                                            6.2        102         23    0.8                                      n-Hexane                                                                              4.3        44          22    12.0                                     iso-Butane                                                                            5.0        99          23    0.6                                      H.sub.2 O                                                                             2.65       4.6         23    28.4                                     ______________________________________                                    

From the above data, the pore size of the calcined product wasdetermined to be greater than about 4.3 Å, as shown by the adsorption ofn-hexane (kinetic diameter of 4.3 Å), but less than about 5.0 Å, asshown by the negligible adsorption of iso-butane (kinetic diameter of5.0 Å).

EXAMPLE 6 Preparation of LiAPSO-44

(a) LiAPSO-44 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide rations of the components of thereaction mixture, of:

1.0-2.0 CHA:0.05-0.2 Li₂ O:0.5-1.0 Al₂ O₃ : 0.5-1.0 P₂ O₅ :0.1-0.6 SiO₂:40-100 H₂ O

where "CHA" denotes cyclohexylamine.

The reaction mixture is digested by placing the reaction mixture in asealed stainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce LiAPSO-44 product.Solids are then recovered by filtration, washed with water and dried inair at room temperature.

The LiAPSO-44 product's chemical analysis shows the LiAPSO-44 productcontains lithium, aluminum, phosphorus and silicon in amounts within thepentagonal compositional area defined by points A, B, C, D and E of FIG.1.

The X-ray powder diffraction pattern of a LiAPSO-44 product ischaracterized by the following data:

    ______________________________________                                        2θ  d(Å)        Relative lntensity                                  ______________________________________                                        9.2-9.6   9.61-9.21       m- vs                                               15.9-16.3 5.57-5.44       vw- m                                               20.5-21.0 4.33-4.23       m- vs                                               24.3-25.1  3.66-3.548     w- m                                                30.5-31.1 2.931-2.876     vw- m                                               ______________________________________                                    

(b) When the calcined LiAPSO-44 is utilized in adsorption capacitystudies using a standard McBain-Bakr gravimetric adsorption apparatusthe measurements are made on a sample after activation at 350° C. in avacuum. The following data are used in the adsorption studies:

    ______________________________________                                                Kinetic    Pressure          Wt. %                                    Adsorbate                                                                             Diameter(Å)                                                                          (Torr)    Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2 3.46       100       -183    13                                       O.sub.2 3.46       70        -183    16                                       n-hexane                                                                              4.3        100         24     2                                       H.sub.2 O                                                                             2.65       4.3         24    15                                       H.sub.2 O                                                                             2.65       20          24    17                                       ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of LiAPSO-44 is about 4.3Å.

PROCESS APPLICATIONS

The LiAPSO compositions of the present invention are, in general,hydrophilic and adsorb water preferentially over common hydrocarbonmolecules such as paraffins, olefins and aromatic species, e.g., benzenezylenes and cumene. Thus the present molecular sieve compositions as aclass are useful as desiccants in such adsorptionseparation/purification processes an natural gas drying, cracked gasdrying. Water is also preferentially adsorbed over the so-calledpermanent gases such as carbon dioxide, nitrogen, oxygen and hydrogen.These LiAPSOs are therefore suitably employed in the drying of reformerhydrogen streams and in the drying of oxygen, nitrogen or air prior toliquifaction.

The present LiAPSO compositions also exhibit novel surface selectivitycharacteristics which render Them useful as catalyst or catalyst basesin a number of hydrocarbon conversion and oxidative combustionreactions. They can be impregnated or otherwise loaded withcatalytically active metals by methods well known in the art and used,for example, in fabricating catalyst compositions having silica oralumina bases. Of the general class, those species having pores largerthan about 4A are preferred for catalytic applications.

Among the hydrocarbon conversion reactions catalyzed by LiAPSOcompositions are cracking, hydrocracking, alkylation for both thearomatic and isoparaffin types, isomerization including zyleneisomerization, polymerization, reforming, hydrogenation,dehydrogenation, transalkylation, dealkylation, hydrodecyclization anddehydrocyclization.

Using LiAPSO catalyst compositions which contain a hydrogenationpromoter such as platinum or palladium, heavy petroleum residual stocks,cyclic stocks and other hydrocrackable charge stocks, can behydrocracked at temperatures in the range of 400° F. to 825° F. (204° C.to 441° C.) using molar ratios of hydrogen to hydrocarbon in the rangeof between 2 and 80, pressures between 10 and 3500 p.s.i.g. (0.171 to24.23 MPa.), and a liquid hourly space velocity (LHSV) of from 0.1 to20, preferably 1.00 to 10.

The LiAPSO catalyst compositions employed in hydrocracking are alsosuitable for use in reforming processes in which the hydrocarbonfeedstocks contact the catalyst at temperatures of from about 700° F. to100° F. (371° C. to 538° C.), hydrogen pressures of from 100 to 500p.s.i.g. (0.791 to 3.448 MPa.), LHSV values in the range of 0.1 to 10and hydrogen to hydrocarbon molar ratios in the range of 1 to 20,preferably between 4 and 12.

These same catalysts, i.e. those containing hydrogenation promoters, arealso useful in hydroisomerization processes in which feedstocks such asnormal paraffins are converted to saturated branched chain isomers.Hydroisomerization is carried out at a temperature of from about 200° F.to 600° F. (93° C. to 316° C.), preferably 300° F. to 550° F. (149° C.to 288° C.) with an LHSV value of from about 0.2 to 1.0. Hydrogen (H) issupplied to the reactor in admixture with the hydrocarbon (Hc) feedstockin molar proportions (H/Hc) of between 1 and 5.

At somewhat higher temperatures, i.e. from about 650° F. to 1000° F.(343° C. to 538° C.), preferably 850° F. to 950° F. (454° C. to 510° C.)and usually at somewhat lower pressures within the range of about 15 to50 p.s.i.g. (205 to 446 KPa.), the same catalyst compositions are usedto hydroisomerize normal paraffins. Preferably the paraffin feedstockcomprises normal paraffins having a carbon number range of C₇ -C₂₀.Contact time between the feedstock and the catalyst is generallyrelatively short to avoid undesirable side reactions such as olefinpolymerization and paraffin cracking. LHSV values in the range of 0.1 to10, preferably 1.0 to 6.0 are suitable.

The unique crystal structure of the present LiAPSO catalysts and theiravailability in a form totally void of alkali metal content (other thanlithium content) favor their use in the conversion of alkylaromaticcompounds, particularly the catalytic disproportionation of toluene,ethylene, trimethyl benzenes, tetramethyl benzenes and the like. In thedisproportionation process, isomerization and transalkylation can alsooccur. Group VIII noble metal adjuvants alone or in conjunction withGroup VI-B metals such as tungsten, molybdenum and chromium arepreferably included in the catalyst composition in amounts of from about3 to 15 weight-% of the overall composition. Extraneous hydrogen can,but need not, be present in the reaction zone which is maintained at atemperature of from about 400° to 750° F. (204° to 399° C.), pressuresin the range of 100 to 200 p.s.i.g. (0.791 to 13.89 MPa.) and LHSVvalues in the range of 0.1 to 15.

Catalytic cracking processes are preferably carried out with LiAPSOcompositions using feedstocks such as gas oils, heavy naphthas,deasphalted crude oil residue, etc., with gasoline being the principaldesired product. Temperature conditions of 850° to 1100° F. (454° to593° C.), LHSV values of 0.5 to 10 and pressure conditions of from about0 to 50 p.s.i.g. (101 to 446 KPa.) are suitable.

Dehydrocyclization reactions employing paraffinic hydrocarbonfeedstocks, preferably normal paraffins having more than b 6 carbonatoms, to form benzene, zylenes, toluene and the like ar carried outusing essentially the same reaction conditions as for catalyticcracking. For these reactions it is preferred to use the LiAPSO catalystin conjunction with a Group VIII non-noble metal cation such as cobaltand nickel.

In catalytic dealkylation wherein it is desired to cleave paraffinicside chains from aromatic nuclei without substantially hydrogenating thering structure, relatively high temperatures in the range of about800°-1000° F. (427°-538° C.) are employed at moderate hydrogen pressuresof about 300-1000 p.s.i.g. (2.17-6.895 MPa.), other conditions beingsimilar to those described above for catalytic hydrocracking. Preferredcatalysts are of the same type described above in connection withcatalytic dehydrocyclization. Particularly desirable dealkylationreactions contemplated herein include the conversion ofmethylnaphthalene to naphthalene and toluene and/or xylenes to benzene.

In catalytic hydrofining, the primary objective is to promote theselective hydrodecomposition of organic sulfur and/or nitrogen compoundsin the feed, without substantially affecting hydrocarbon moleculestherein. For this purpose it is preferred to employ the same generalconditions described above for catalytic hydrocracking, and catalysts ofthe same general nature. described in connection with dehydrocyclizationoperations. Feedstocks include gasoline fractions, kerosenes, jet fuelfractions, diesel fractions, light and heavy gas oils, deasphalted crudeoil residua and the like. Any of these may contain up to about 5weight-percent of sulfur and up to about 3 weight-percent of nitrogen.

Similar conditions can be employed to effect hydrofining, i.e.,denitrogenation and desulfurization, of hydrocarbon feeds containingsubstantial proportions of organonitrogen and organosulfur compounds. Itis generally recognized that the presence of substantial amounts of suchconstituents markedly inhibits the activity of hydrocracking catalysts.Consequently, it is necessary to operate at more extreme conditions whenit is desired to obtain the same degree of hydrocracking conversion perpass on a relatively nitrogenous feed than with a feed containing lessorganonitrogen compounds. Consequently, the conditions under whichdenitrogenation, desulfurization and/or hydrocracking can be mostexpeditiously accomplished in any given situation are necessarilydetermined in view of the characteristics of the feedstocks, inparticular the concentration of organonitrogen compounds in thefeedstock. As a result of the effect of organonitrogen compounds on thehydrocracking activity of these compositions it is not at all unlikelythat the conditions most suitable for denitrogenation of a givenfeedstock having a relatively high organonitrogen content with minimalhydrocracking, e.g., less than 20 volume percent of fresh feed per pass,might be the same as those preferred for hydrocracking another feedstockhaving a lower concentration of hydrocracking inhibiting constituentse.g., organonitrogen compounds. Consequently, it has become the practicein this art to establish the conditions under which a certain feed is tobe contacted on the basis of preliminary screening tests with thespecific catalyst and feedstock.

Isomerization reactions are carried out under conditions similar tothose described above for reforming, using somewhat more acidiccatalysts. Olefins are preferably isomerized at temperatures of500°-900° F. (260°-482° C.), while paraffins, naphthenes and alkylaromatics are isomerized at temperatures of 700°-1000° F. (371°-538°C.). Particularly desirable isomerization reactions contemplated hereininclude the conversion of n-heptane and/or n-octane to isoheptanes,iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane,meta-xylene and/or ortho-xylene to paraxylene, 1-butene to 2-buteneand/or isobutene, n-hexane to isohexene, cyclohexene tomethylcyclopentene etc. The preferred form of the catalyst is acombination of the LiAPSO with polyvalent metal compounds (such assulfides) of metals of Group II-A, Group II-B and rare earth metals. Foralkylation and dealkylation processes the LiAPSO compositions havingpores of at least 5Å are preferred. When employed for dealkylation ofalkyl aromatics, the temperature is usually at least 350° F. (177° C.)and ranges up to a temperature at which substantial cracking of thefeedstock or conversion products occurs, generally up to about 700° F.(371° C.). The temperature is preferably at least 450° F. (232° C.) andnot greater than the critical temperature of the compound undergoingdealkylation. Pressure conditions are applied to retain at least thearomatic feed in the liquid state. For alkylation the temperature can beas low as 250° F. (121° C.) but is preferably at least 350° F. (177°C.). In the alkylation of benzene, toluene and zylene, the preferredalkylating agents are olefins such as ethylene and propylene.

The following example is provided to further illustrate the use of theLiAPSOs of the invention in one of the processes discussed above, but isnot intended to be limitative of the possible uses of the LiAPSOs.

EXAMPLE 7 Cracking tests on LiAPSO-34

The n-butane cracking activity of the LiAPSO-34 prepared in Example 5above was tested in a bench-scale apparatus, in which the reactor was acylindrical quartz tube 254 mm. in length and 10.3 mm. in internaldiameter. This reactor was loaded with the as-synthesized LiAPSO-34,which was in the form of particles having sizes of 20-40 U.S. mesh. TheLiAPSO-34 was then calcined in situ by heating from ambient temperatureto 500° C. under helium, and then holding the sample at 500° C. underhelium for 1 hour; the weight of the activated mixture in the reactorwas 2.70 grams.

A feedstock comprising a helium/n-butane mixture containing 2 molepercent of n-butane was then passed through the reactor at 500° C. andat a rate of 50mL/min. The reactor effluent was analyzed after 10minutes of on-stream operation using conventional gas chromatographytechniques. The resultant data showed a pseudo-first-order rate constant(k_(A)) of 0.2.

We claim:
 1. Crystalline molecular sieves having three-dimensionalmicroporous framework structures of LiO₂, AlO₂, PO₂, and SiO₂tetrahedral units having an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(Li.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Li_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero (0) to about 0.3; and "w", "x", "y" and "z" represent the molefraction of lithium, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides, said mole fractions being such that theyare within the pentagonal compositional area defined by points A, B, C,D and E of FIG. 1, The crystalline molecular sieves having acharacteristic X-ray powder diffraction pattern which contains at leastthe d-spacings set forth in one of the following Tables L and LA,

                  TABLE L                                                         ______________________________________                                        (LiAPSO-34)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.3-9.8      9.51-9.03 m-vs                                                   12.6-13.2    7.03-6.71 w-m                                                    15.8-16.3    5.61-5.44 vw-m                                                   20.25-21.2   4.39-4.19 w-vs                                                   24.8-25.4     3.59-3.507                                                                             vw-m                                                   30.0-30.9    2.979-2.894                                                                             vw-m                                                   ______________________________________                                    

                  TABLE LA                                                        ______________________________________                                        (LiAPSO-34)                                                                                       Relative Intensity                                        2θ     d(Å)                                                                             100 × I/I.sub.o                                     ______________________________________                                        9.56         9.25   100                                                       12.9         6.87   15                                                        14.1         6.26   18                                                        16.1         5.52   48                                                        18.0         4.92   23                                                        20.6         4.31   89                                                        22.3         3.99   5                                                         23.2         3.84   6                                                         25.3         3.53   26                                                        25.9         3.44   17                                                        27.7         3.22   7                                                         28.4         3.14   7                                                         29.7         3.01   5                                                         30.6         2.92   35                                                        31.3         2.86   21                                                        34.5         2.60   7                                                         36.4         2.47   5                                                         39.7         2.27   4                                                         43.5         2.08   5                                                         47.7         1.91   5                                                         49.1         1.86   7                                                         51.1         1.79   4                                                         53.3         1.72   3                                                         54.7         1.68   3                                                         ______________________________________                                    


2. Crystalline molecular sieves according to claim 1 wherein the molefractions of lithium, aluminum, phosphorus and silicon present astetrahedral oxides are with the hexagonal compositional area defined bypoints a, b, c, d, e and f of FIG.
 2. 3. The crystalline molecularsieves according to claim 1 or claim 2 wherein "m" is not greater thanabout 0.15.
 4. The crystalline molecular sieves of claim 1 or 2 whereinw+z is not greater than about 0.20.
 5. Process for preparing crystallinemolecular sieves having three-dimensional microporous frameworkstructures of LiO₂, AlO₂, PO₂ and SiO₂ tetrahedral units having anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(Li.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Li_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of lithium, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides, said mole fractions being such that theyare within the pentagonal compositional area defined by points A, B, C,D, and E of FIG. 1, the crystalline molecular sieves having acharacteristic X-ray powder diffraction pattern which contains at leastthe d-spacings set forth in one of the following Tables L and LA,

                  TABLE L                                                         ______________________________________                                        (LiAPSO-34)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.3-9.8      9.51-9.03 m-vs                                                   12.6-13.2    7.03-6.71 w-m                                                    15.8-16.3    5.61-5.44 vw-m                                                   20.25-21.2   4.39-4.19 w-vs                                                   24.8-25.4     3.59-3.507                                                                             vw-m                                                   30.0-30.9    2.979-2.894                                                                             vw-m                                                   ______________________________________                                    

                  TABLE LA                                                        ______________________________________                                        (LiAPSO-34)                                                                                       Relative Intensity                                        2θ     d(Å)                                                                             100 × I/I.sub.o                                     ______________________________________                                        9.56         9.25   100                                                       12.9         6.87   15                                                        14.1         6.26   18                                                        16.1         5.52   48                                                        18.0         4.92   23                                                        20.6         4.31   89                                                        22.3         3.99   5                                                         23.2         3.84   6                                                         25.3         3.53   26                                                        25.9         3.44   17                                                        27.7         3.22   7                                                         28.4         3.14   7                                                         29.7         3.01   5                                                         30.6         2.92   35                                                        31.3         2.86   21                                                        34.5         2.60   7                                                         36.4         2.47   5                                                         39.7         2.27   4                                                         43.5         2.08   5                                                         47.7         1.91   5                                                         49.1         1.86   7                                                         51.1         1.79   4                                                         53.3         1.72   3                                                         54.7         1.68   3                                                         ______________________________________                                    

the process comprising providing a reaction mixture composition at aneffective temperature and for an effective time sufficient to producesaid molecular sieves, said reaction mixture composition being expressedin terms of molar oxide ratios as follows:

    aR:(Li.sub.s Al.sub.t P.sub.u Si.sub.v)O.sub.2 ;bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of "R" andis an effective amount greater than zero to about 6; "b" has a value ofbetween zero and about 500; and "s", "t", "u" and "v" represent the molefractions, respectively, of lithium, aluminum, phosphorus and silicon inthe (Li_(s) Al_(t) P_(u) Si_(v))O₂ constituent, and each has a value ofat least 0.01.
 6. Process according to claim 5 wherein "s", "t", "u" and"y" are within the area defined by points F, G, H, I and J of FIG.
 3. 7.Process according to claim 5 wherein "a" is not greater than about 0.5.8. Process according to claim 5 wherein "b" is from about 2 to about
 5009. Process according to claim 8 wherein "b" is from about 2 to about300.
 10. Process according to claim 9 wherein "b" is not greater thanabout
 20. 11. Process according to claim 10 wherein "b" is not greaterthan about
 10. 12. Process according to claim 5 wherein the source ofphosphorus in the reaction mixture is orthophosphoric acid.
 13. Processaccording to claim 5 wherein the source of phosphorus in the reactionmixture is orthophosphoric acid and the source of aluminum is at leastone compound selected from the group consisting of pseudo-boehmite andaluminum alkoxides.
 14. Process according to claim 13 wherein thealuminum alkoxide is aluminum isopropoxide.
 15. Process according toclaim 5 wherein the source of lithium is selected from the groupconsisting of oxides, hydroxides, alkoxides, chlorides, bromides,iodides, sulfates, nitrates, carboxylates and mixtures thereof. 16.Process according to claim 5 wherein the source of lithium is lithiumorthophosphate.
 17. Process according to claim 5 wherein the siliconsource is silica.
 18. Process according to claim 5 wherein the silicasource is a tetraalkyl orthosilicate.
 19. Process according to claim 5wherein the organic templating agent is a quaternary ammonium orquaternary phosphonium compound having the formula:

    R.sub.4 X.sup.+

wherein X is nitrogen or phosphorus and each R is an alkyl or aryl groupcontaining from 1 to 8 carbon atoms.
 20. Process according to claim 5wherein the organic templating agent is an amine.
 21. Process accordingto claim 5 wherein the templating agent is selected from the groupconsisting of tetrapropylammonium ion; tetraethylammonium ion;tripropylamine; triethylamine; triethanolamine; piperidine;cyclohexylamine; 2-methyl pyridine; N,N-dimethylbenzylamine;N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine;1,4-diaziabicyclo-(2,2,2) octane; N-methyldiethanolamine;N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine;N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine;quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;tetramethylammonium ion; tetrabutylammonium ion; tetrapentylammoniumion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropylamine;t-butylamine; ethylenediamine; pyrrolidine; 2-imidazolidone;di-n-propylamine; and a polymeric quaternary ammonium salt _(x) whereinx is a value of at least
 2. 22. Molecular sieves prepared by calcining,at a temperature sufficiently high to remove at least some of anyorganic templating agent present in the intracrystalline pore system,the crystalline molecular sieves having three-dimensional microporousframework structures of LiO₂, AlO₂, PO₂ and SiO₂ tetrahedral unitshaving an empirical chemical composition on an anhydrous basis expressedby the formula:

    mR:(Li.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Li_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of lithium, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides, said mole fractions being such that theyare within the pentagonal compositional area defined by points A, B, C,D, and E of FIG. 1, the calcined crystalline molecular sieves having acharacteristic X-ray powder diffraction pattern which contains at leastthe d-spacings set forth in one of the following Tables L and LB,

                  TABLE L                                                         ______________________________________                                        (LiAPSO-34)                                                                   2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.3-9.8      9.51-9.03 m-vs                                                   12.6-13.2    7.03-6.71 w-m                                                    15.8-16.3    5.61-5.44 vw-m                                                   20.25-21.2   4.39-4.19 w-vs                                                   24.8-25.4     3.59-3.507                                                                             vw-m                                                   30.0-30.9    2.979-2.894                                                                             vw-m                                                   ______________________________________                                    

                  TABLE LB (LiAPSO-34                                             ______________________________________                                        (LiAPSO-34)                                                                                            Relative Intensity                                   2θ  d(Å)       100 × I/Io                                     ______________________________________                                         9.67     9.15           100                                                  13.1      6.78            22                                                  14.2      6.22            2                                                   16.2      5.46            11                                                  18.0      4.92            8                                                   19.2      4.62            2                                                   20.8      4.27            27                                                  22.3      4.00            2                                                   23.3      3.82            3                                                   25.2      3.53            7                                                   26.1      3.41            7                                                   27.9      3.20            2                                                   28.4      3.14            1                                                   30.9      2.90            14                                                  31.3      2.86            7 (shoulder)                                        34.8      2.58            3                                                   36.3      2.47            2                                                   43.2      2.09            2                                                   48.1      1.89            2                                                   49.3      1.85            2                                                   51.1      1.79            2                                                   53.7      1.71            1                                                   54.8      1.68            1                                                   ______________________________________                                    